JP5396694B2 - Crosslinkable prepolymer and production method and use thereof - Google Patents

Description

  The present invention relates to a crosslinkable prepolymer, a method for producing the crosslinkable prepolymer, and uses of the crosslinkable prepolymer.

  Regarding a polymer having a polyaryl ether structure in the main chain, for example, in Patent Document 1 below, a compound having a phenolic hydroxyl group or a fluorine-substituted aromatic ring and a crosslinkable functional group, a fluorine-substituted aromatic compound, and a phenolic hydroxyl group are 3 There has been proposed a method for producing a crosslinkable prepolymer having a polyaryl ether structure in the main chain and having a crosslinkable functional group introduced by condensing at least one compound.

JP 2005-105115 A

Although the cured product composed of the crosslinkable prepolymer of Patent Document 1 is excellent in heat resistance, the oil repellency and water repellency are not always sufficient depending on applications.
The present invention has been made in view of the above circumstances, and provides a prepolymer capable of forming a cured product which is excellent in heat resistance and excellent in oil repellency and water repellency, and a production method and use thereof.

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]

[Wherein, n represents an integer of 0 to 2; a and b each independently represents an integer of 0 to 3; Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms; When a plurality of Rf ¹ or Rf ² are present, they may be the same or different from each other; F in the aromatic ring indicates that all the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms. Represent. ]

The first aspect of the present invention is a polymer having a polyaryl ether structure in the main chain, having a crosslinkable functional group, and being substituted with a halogen atom capable of reacting with a phenolic hydroxyl group in the main chain. precursor having an aromatic ring "and (P2), an alcohol (Q) represented by the following formula (II), a crosslinked prepolymer obtained by reacting in the presence of a dehydrofluorination agent ,
The precursor (P2) is either or both of the following compound (Y-1) and the following compound (Y-2), the fluorine-containing aromatic compound (B) represented by the general formula (1), A crosslinkable prepolymer, which is a precursor (P21) obtained by subjecting a compound (C) having three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent .
Compound (Y-1): any of compound (Y-1-1) having one crosslinkable functional group and one phenolic hydroxyl group and compound (Y-1-2) having two crosslinkable functional groups and two phenolic hydroxyl groups Either or both.
Compound (Y-2): A compound having a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”.

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]

The second aspect of the present invention is a polymer having a polyaryl ether structure in the main chain and a precursor having “an aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain ( P1) and the alcohol (Q) represented by the general formula (II) are reacted in the presence of a dehydrofluorinating agent, and the following compounds (Y-1) and (Y-2): A crosslinkable prepolymer obtained by introducing a crosslinkable functional group by subjecting one or both to a condensation reaction in the presence of a dehydrofluorinating agent , wherein the precursor (P1) has the general formula (1) ) And a precursor (P11) obtained by subjecting a compound (C) having 3 or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent. A crosslinkable process characterized by It is a polymer.
Compound (Y-1): any of compound (Y-1-1) having one crosslinkable functional group and one phenolic hydroxyl group and compound (Y-1-2) having two crosslinkable functional groups and two phenolic hydroxyl groups Either or both.
Compound (Y-2): A compound having a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”.

In the third aspect of the present invention, the fluorine-containing aromatic compound (B) represented by the general formula (1) and the compound (C) having three or more phenolic hydroxyl groups are present in the presence of a dehydrofluorinating agent. a step (S1) to a condensation reaction under, one or both of the following compound (Y-1) and the following compound (Y-2), to a condensation reaction in the presence of a dehydrofluorination agent, crosslinkable functional groups And a step (S3) of introducing a side chain by reacting the alcohol (Q) represented by the general formula (II) in the presence of a dehydrofluorinating agent. This is a method for producing a crosslinkable prepolymer.
Compound (Y-1): any of compound (Y-1-1) having one crosslinkable functional group and one phenolic hydroxyl group and compound (Y-1-2) having two crosslinkable functional groups and two phenolic hydroxyl groups Either or both.
Compound (Y-2): A compound having a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”.

The 4th form of this invention is a hardened | cured material formed by hardening the crosslinkable prepolymer of either the 1st or 2nd form.
A fifth aspect of the present invention is a coating composition comprising the crosslinkable prepolymer of any one of the first and second aspects and a solvent.
In the sixth aspect of the present invention, the coating composition of the fifth aspect is applied to a substrate to form a wet film, the solvent in the wet film is removed, and then wet or simultaneously with the removal of the solvent. It is a cured film obtained by curing the crosslinkable prepolymer in the film.
The seventh aspect of the present invention is an article having the cured film of the sixth aspect.

According to the present invention, it is possible to obtain a crosslinkable prepolymer capable of forming a cured product having excellent heat resistance and excellent oil repellency and water repellency.
The cured product of the present invention can simultaneously achieve excellent heat resistance, oil repellency and water repellency.
According to the coating composition of the present invention, a cured film having excellent heat resistance and excellent oil repellency and water repellency can be formed.
The cured film of the present invention can simultaneously achieve excellent heat resistance, oil repellency and water repellency.
The article of the present invention is excellent in heat resistance and has a film excellent in oil repellency and water repellency.

The obtained cured film simultaneously satisfies a low dielectric constant, a low water absorption rate and a high heat resistance. For this reason, when it uses for insulating films, such as memory | storage elements, such as various memories, and theoretical circuit elements, such as a microprocessor, the improvement of the electrical property of an element can be aimed at. In addition, since it is less susceptible to moisture and heat, it can improve reliability as well as electrical characteristics.
Moreover, the obtained cured film is excellent in alkali resistance. That is, even when exposed to an alkaline atmosphere, excellent water repellency and oil repellency are maintained.
Furthermore, since the crosslinkable prepolymer according to the present invention can form a cured film having excellent flexibility, a film resistant to external forces such as bending can be obtained. A thick film can also be easily formed.

<Crosslinkable prepolymer>
The crosslinkable prepolymer of the present invention (hereinafter sometimes simply referred to as a prepolymer) is a polymer having a polyaryl ether structure in the main chain, having a crosslinkable functional group, and having the above general formula ( It has a side chain represented by I).

[Main chain]
In the present invention, the “polyaryl ether structure” means a polymer structure formed by repeating a structure in which two aromatic rings are bonded via an ether bond (—O—). The “aromatic ring” in the present invention means a ring structure in a cyclic organic compound having aromaticity, and includes those having an arbitrary substituent unless otherwise specified.
“Having a polyaryl ether structure in the main chain” means that in each aromatic ring constituting the polyaryl ether structure, two or more carbon atoms constituting the ring are carbon chains constituting the main chain (however, 2 The ether bond between the two aromatic rings is regarded as a part of the carbon chain constituting the main chain, that is, the ether bond may be interposed between the two aromatic rings, and so on. It means that.
In the crosslinkable prepolymer of the present invention, the carbon chain constituting the main chain may be branched. In the present invention, even a branched carbon chain (branched chain) includes a part containing a polyaryl ether structure, or a part containing "an aromatic ring in which two or more carbon atoms are carbon atoms in the carbon chain" Is regarded as a part of the main chain, and the terminal part not including these structures is referred to as a “side chain”.

Halogen in which one of two aromatic rings bonded via an ether bond in the polyaryl ether structure of the main chain is substituted with a halogen atom for some or all of the hydrogen atoms bonded to the aromatic ring A substituted aromatic ring is preferred.
The halogen atom in the halogen-substituted aromatic ring is preferably a fluorine atom. The halogen-substituted aromatic ring is preferably a perfluoroaromatic ring in which all of the hydrogen atoms bonded to the aromatic ring are substituted with halogen atoms, and all of the hydrogen atoms are substituted with fluorine atoms. More preferred.
The main chain may have another aromatic ring other than the aromatic ring constituting the polyaryl ether structure. The other aromatic ring is preferably the halogen-substituted aromatic ring, and more preferably the perfluoroaromatic ring.

[Crosslinkable functional group]
The crosslinkable functional group in the present invention does not substantially react at the time of producing the prepolymer, and gives external energy at the time of producing a cured product such as a film, a film or a molded product, or at any time after production. A reactive functional group that reacts to cause cross-linking or chain extension between prepolymer molecules.
Examples of the external energy include heat, light, and electron beam. These may be used in combination. When heat is used as external energy, a reactive functional group that reacts at a temperature of 40 ° C to 500 ° C is preferable. If the reaction temperature is too low, stability during storage of the prepolymer or the coating composition containing the prepolymer cannot be ensured, and if it is too high, thermal decomposition of the prepolymer itself occurs during the reaction. It is preferable that it exists in. More preferably, it is 60 degreeC-400 degreeC, and 70 degreeC-350 degreeC is the most preferable.
Moreover, when using light (actinic radiation) as external energy, it is preferable to contain a photosensitizer in the prepolymer or the coating composition containing the prepolymer. In this case, the prepolymer in the exposed area can be made high molecular weight by selectively irradiating actinic radiation in the exposure process, and external energy such as actinic radiation or heat can be applied after the exposure and development processes as necessary. The prepolymer can be further increased in molecular weight.

  Specific examples of the crosslinkable functional group include vinyl group, allyl group, methacryloyl (oxy) group, acryloyl (oxy) group, vinyloxy group, trifluorovinyl group, trifluorovinyloxy group, ethynyl group, 1-oxocyclopenta Examples include -2,5-dien-3-yl group, cyano group, alkoxysilyl group, diarylhydroxymethyl group, hydroxyfluorenyl group and the like. A vinyl group, a methacryloyl (oxy) group, an acryloyl (oxy) group, a trifluorovinyloxy group, and an ethynyl group are preferable because the reactivity is high and a high crosslinking density is obtained, and the resulting cured product has good heat resistance. From the point of having, a vinyl group and an ethynyl group are most preferable. The methacryloyl (oxy) group means a methacryloyl group or a methacryloyloxy group, and the same applies to an acryloyl (oxy) group.

The crosslinkable functional group may be in the main chain or in the side chain. “The crosslinkable functional group is present in the main chain” means that one or more carbon atoms constituting the crosslinkable functional group (which may contain an etheric oxygen atom) include the main chain. It means a carbon atom in the constituting carbon chain.
From the viewpoint of easy availability of the raw material, it is preferable that the crosslinkable functional group is in the side chain and the main chain does not have the crosslinkable functional group.

  The content of the crosslinkable functional group in the prepolymer of the present invention is preferably from 0.1 to 4 mmol, more preferably from 0.2 to 3 mmol, based on 1 g of the prepolymer. By setting the content to 0.1 mmol or more, the heat resistance and solvent resistance of the cured product can be increased, and by setting the content to 4 mmol or less, brittleness can be easily reduced.

[Side Chains Represented by General Formula (I)]
In the general formula (I), R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms, and may contain an etheric oxygen atom. The fluorine-containing alkyl group as R ^f means one in which part or all of the hydrogen atoms bonded to the carbon atom of the alkyl group are substituted with fluorine atoms. The fluorine-containing alkyl group may be a chain alkyl group or a cycloalkyl group.
R ^f is preferably linear, branched or cyclic. R ^f is preferably a perfluoroalkyl group in which all of the hydrogen atoms bonded to the carbon atoms of the alkyl group are substituted with fluorine atoms.
Of the side chains represented by the general formula (I), the linear one is preferably those represented by the following general formula (I-1) or the following general formula (I-2). In the following general formula (I-1), m represents an integer of 1 to 5, R ^fa represents a fluorine-containing alkyl group having 4 to 50 carbon atoms, and may contain an etheric oxygen atom. m is more preferably an integer of 1 to 3.
More preferable examples of the side chain represented by the following general formula (I-1) include a monovalent group represented by the following general formula (I-1-1) or the following general formula (I-1-2). The monovalent group represented is mentioned.

  Moreover, as a branched chain thing among the side chains represented by the said general formula (I), the monovalent group represented by the following general formula (I-3) or (I-4) is preferable.

  Moreover, as a cyclic | annular thing among the side chains represented by the said general formula (I), the monovalent group represented by the following formula (I-5), (I-6) or (I-7) is preferable.

The position at which the side chain represented by the general formula (I) is introduced is not particularly limited, but it is preferable in production that the side chain is bonded to the halogen-substituted aromatic ring in the main chain. That is, it is preferable that a halogen-substituted aromatic ring exists in the main chain, and a side chain represented by the general formula (I) is bonded to the aromatic ring.
The halogen-substituted aromatic ring to which the side chain is bonded may be an aromatic ring constituting a polyaryl ether structure, or may be another aromatic ring other than that. From the viewpoint of easy production of the prepolymer, it is more preferable that the side chain represented by the general formula (I) is bonded to the latter, that is, the halogen-substituted aromatic ring not constituting the polyaryl ether structure. The halogen-substituted aromatic ring to which the side chain is bonded is more preferably a perfluoroaromatic ring.

The “side chain represented by the general formula (I)” present in one molecule of the prepolymer may be one type or two or more types.
The content of the “side chain represented by the general formula (I)” in the prepolymer of the present invention is preferably 0.01 to 1 g, more preferably 0.05 to 0.5 g, relative to 1 g of the prepolymer. When this content is at least the lower limit of the above range, the effect of improving water repellency and oil repellency can be obtained satisfactorily, and when it is at most the upper limit, heat resistance is good.

<Prepolymer production method>
The prepolymer of the present invention comprises a fluorine-containing aromatic compound (B) represented by the general formula (1) and a compound (C) having 3 or more phenolic hydroxyl groups in the presence of a dehydrofluorinating agent. The step (S1) of condensation reaction, the compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group, the crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” A step (S2) of introducing a crosslinkable functional group by performing a condensation reaction in the presence of a dehydrofluorinating agent on one or both of the compounds (Y-2) having the above formula (II). The step (S3) of reacting the alcohol (Q) in the presence of a dehydrofluorinating agent to introduce a side chain can be produced. In the following description, compound (Y-1) and compound (Y-2) may be collectively referred to as compound (Y).

  More specifically, the method of performing the step (S3) after performing the step (S1) and the step (S2), or the step (S2) after performing the step (S1) and the step (S3). The method of carrying out is preferred. However, performing step (S1) and step (S2) may be performed after step (S1) is performed, step (S2) may be performed, and step (S1) and step (S2) are performed simultaneously. Also good. The same applies to the steps (S1) and (S3).

  Steps (S1), (S2), and (S3) are all condensation reactions performed in the presence of a dehydrofluorinating agent (hereinafter also referred to as a deHF agent). In addition, all of these condensation reactions may be reacted in one step, or may be performed in multiple steps. Moreover, after reacting a specific compound preferentially among the reaction raw materials, another compound may be subsequently reacted. When the condensation reaction is performed in multiple stages, the intermediate product obtained in the middle may be separated from the reaction system and purified, and then used for the subsequent reaction (condensation reaction). In the reaction field, the raw material compounds may be charged all at once, may be charged continuously, or may be charged intermittently.

[Production Method Using Precursor (P1)]
Further, as a method for producing the prepolymer of the present invention, a polymer having a polyaryl ether structure in the main chain and having “an aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain. It is preferable to react the precursor (P1) with the alcohol (Q) represented by the general formula (II) in the presence of a dehydrofluorinating agent, and further introduce a crosslinkable functional group. Specifically, the precursor (P1) is obtained by performing the step (S1), the precursor (P1) and the alcohol (Q) are subjected to a condensation reaction, and then the compound (Y) is subjected to a condensation reaction. The prepolymer of the present invention is obtained.
In this production method, the molecular weight of the prepolymer can be easily controlled by producing the precursor (P1) first. Moreover, when the reactivity of alcohol (Q) is low compared with compound (Y), it is suitable for reacting a desired amount of alcohol (Q). That is, it is preferable in that the introduction of a desired amount of the side chain represented by the general formula (I) can be easily controlled. Depending on the selection of the raw material, when a crosslinkable functional group is introduced, the storage stability of the prepolymer may decrease due to the progress of the crosslinking reaction. In this case, the intermediate product may be stored at a stage where the crosslinkable functional group is not introduced, and it may be expected that the yield of the prepolymer is improved.
More specifically, as the precursor (P1), a fluorine-containing aromatic compound (B) represented by the general formula (1) and a compound (C) having three or more phenolic hydroxyl groups are defluorinated. It is preferable to use a precursor (P11) obtained by a condensation reaction in the presence of a hydrogenation agent. That is, after carrying out the step (S1), it is preferable to carry out the step (S3) to introduce the side chain represented by the general formula (I), and then carry out the step (S2) to introduce a crosslinkable functional group. .

[Production method using precursor (P2)]
Another method for producing the prepolymer of the present invention is a polymer having a polyaryl ether structure in the main chain, having a crosslinkable functional group and having “a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain. It is also preferable to react the precursor (P2) having the “aromatic ring substituted with” with the alcohol (Q) represented by the general formula (II) in the presence of a dehydrofluorinating agent. Specifically, the precursor (P2) is obtained by performing the steps (S1) and (S2), and the precursor (P2) and the alcohol (Q) are subjected to a condensation reaction, whereby the prepolymer of the present invention is obtained. can get. This production method is preferable in that the production process of the prepolymer is easily simplified by producing the precursor (P2) first.
More specifically, as the precursor (P2), the compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group, the crosslinkable functional group and “a fluorine atom capable of reacting with a phenolic hydroxyl group” are substituted. Either or both of the compound (Y-2) having an “aromatic ring”, the fluorine-containing aromatic compound (B) represented by the general formula (1), and a compound having three or more phenolic hydroxyl groups (C It is preferable to use a precursor (P21) obtained by a condensation reaction in the presence of a dehydrofluorinating agent. That is, it is preferable to implement a step (S3) and introduce a side chain after carrying out the step (S1) and the step (S2) to introduce a crosslinkable functional group. The precursor (P2) can also be obtained by reacting the compound (Y) after obtaining the precursor (P1).

The “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” is preferably an aromatic ring in which two or more of the hydrogen atoms bonded to the aromatic ring are substituted with a halogen atom, It is preferred that all of the hydrogen atoms are substituted with halogen atoms. The halogen atom is preferably a fluorine atom, and the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” is most preferably a perfluoroaromatic ring. Examples of the perfluoroaromatic ring include perfluorophenyl and perfluorobiphenyl.
Furthermore, the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” is introduced into the prepolymer by the fluorine-containing aromatic compound (B) or the compound (Y-2). Therefore, the side chain represented by the general formula (I) is introduced into an aromatic ring derived from the fluorine-containing aromatic compound (B) or the compound (Y-2).

  In the condensation reaction in the method for producing a prepolymer of the present invention, as represented by the following formula (2), a phenoxy group derived from a phenolic hydroxyl group is bonded to a fluorine atom of the fluorinated aromatic compound (B). An ether bond is generated by a reaction mechanism in which a carbon atom and / or a carbon atom to which a fluorine atom (or halogen atom) of (Y-2) is bonded is attacked and then the fluorine atom (or halogen atom) is eliminated. When the compound (C) and / or (Y-1) has two phenolic hydroxyl groups in the ortho positional relationship, the dioxin skeleton is represented by the same reaction mechanism as shown in the following formula (3). May generate.

By using the compound (Y-1) or (Y-2) having a crosslinkable functional group as a monomer for producing the prepolymer of the present invention, a prepolymer having a crosslinkable functional group introduced therein can be obtained. As a result, when the prepolymer of the present invention is cured, the crosslinking or chain extension reaction between the prepolymer molecules proceeds, and the heat resistance is greatly improved. Moreover, the effect that the solvent resistance of hardened | cured material improves is also acquired.
Further, by using the compound (C) having three or more phenolic hydroxyl groups, a prepolymer having a branched structure introduced into the polymer chain and a three-dimensional molecular structure can be obtained. Thereby, it is possible to introduce a crosslinking group or a side chain represented by the above formula (I) without lowering the molecular weight of the prepolymer.
Furthermore, the flexibility in the cured product can be improved by using the fluorine-containing aromatic compound (B) represented by the general formula (1). The prepolymer using the compound (B) as a monomer has a higher ether bond density than a fluorine-containing aromatic polymer produced using a fluorine-containing aromatic compound having a branched structure as a monomer. The flexibility of the main chain is improved. Thereby, good flexibility is obtained in the cured product of the prepolymer of the present invention. Further, the good flexibility of the cured product is particularly advantageous when the cured product is in the form of a cured film.

[Fluorine-containing aromatic compound (B)]
The fluorine-containing aromatic compound (B) is a fluorine-containing aromatic compound represented by the general formula (1). That is, the fluorine-containing aromatic compound (B) is a compound having “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”. The fluorine-containing aromatic compound (B) is also a compound having an aromatic ring to which the side chain represented by the general formula (I) can be bonded in the condensation reaction with the alcohol (Q).
In this formula (1), Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms, preferably 3 or less carbon atoms. If Rf ¹ there are a plurality in one of the fluorinated aromatic compound (B), they may be the same or may be different. Similarly, when there are a plurality of Rf ² , they may be the same or different.
The fluorine-containing alkyl group as Rf ¹ or Rf ² means one in which part or all of the hydrogen atoms bonded to the carbon atom of the alkyl group are substituted with fluorine atoms. From the viewpoint of heat resistance, a perfluoroalkyl group is preferred. Specific examples include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

When Rf ¹ and Rf ² are increased, it becomes difficult to produce the fluorine-containing aromatic compound (B). Accordingly, the number of Rf ¹ (a in the formula) is 0 to 3, preferably 0 to 2, and most preferably 0.
The number of Rf ² (n b in the formula) is 0 to 6, preferably 0 to 2, and most preferably 0.
In the said General formula (1), n is an integer of 0-2, 0 or 1 is preferable and 1 is the most preferable.

As specific examples of the fluorine-containing aromatic compound (B), the following compounds can be preferably exemplified.
perfluorobenzene, perfluorotoluene, perfluoroxylene when n = 0; perfluorobiphenyl when n = 1; perfluoroterphenyl when n = 2; perfluoro (1, 3, 3 when n = 3 5-triphenylbenzene) and perfluoro (1,2,4-triphenylbenzene). In particular, perfluorobenzene, perfluorobiphenyl, perfluoro (1,3,5-triphenylbenzene), and perfluoro (1,2,4-triphenylbenzene) are preferable. These may be used alone or in combination of two or more. In the case of n = 3, a branched structure is introduced into the prepolymer, so that the heat resistance of the cured product can be improved.
Perfluorobiphenyl is most preferable as the fluorine-containing aromatic compound (B) in that the obtained cured product is excellent in the balance between the dielectric constant and heat resistance and the flexibility of the cured product is increased.

[Compound (C)]
The compound (C) is a compound having 3 or more phenolic hydroxyl groups. In the present invention, those having a crosslinkable functional group are not included in the compound (C).
Specific examples of the compound (C) include trihydroxybenzene, trihydroxybiphenyl, trihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) benzene, tetrahydroxybenzene, Examples thereof include tetrahydroxybiphenyl, tetrahydroxybinaphthyl, tetrahydroxyspiroindanes and the like. Since the flexibility of the obtained cured film becomes high, the compound (C) is preferably a compound having three phenolic hydroxyl groups. Among these, 1,1,1-tris (4-hydroxyphenyl) ethane and trihydroxybenzene are more preferable.

  The precursor (P11) is produced by subjecting the compound (B) and the compound (C) to a condensation reaction in the presence of a deHF agent. Thereafter, the side chain represented by the general formula (I) and the crosslinkable functional group are introduced. For introducing the crosslinkable functional group, it is preferable to use the compound (Y-1) or the compound (Y-2).

The precursor (P21) is produced by either or both of the following methods (i) and (ii).
(I) A method in which the compound (B), the compound (C) and the compound (Y-1) are subjected to a condensation reaction in the presence of a deHF agent.
(Ii) A method in which the compound (B), the compound (C) and the compound (Y-2) are subjected to a condensation reaction in the presence of a deHF agent.
In addition, when manufacturing a precursor (P21) by both said (i) and (ii), a fluorine-containing aromatic compound (B), a compound (C), a compound (Y-1), and a compound (Y-2) ) In the presence of a deHF agent.
When the side chain represented by the above general formula (I) is introduced into the precursor (P21), the main chain is “an aromatic in which part or all of the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms”. A prepolymer in which the side chain represented by the general formula (I) is bonded to the fluorine-containing aromatic ring is obtained.

[Compound (Y-1)]
The compound (Y-1) has a crosslinkable functional group and a phenolic hydroxyl group. The compound (Y-1) does not have “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”.
As the compound (Y-1), a compound (Y-1-1) having one phenolic hydroxyl group and a compound (Y-1-2) having two phenolic hydroxyl groups are preferable. (Y-1-1) works as a monofunctional compound, and when this is used, a prepolymer having a crosslinkable functional group in the side chain is obtained. (Y-1-2) works as a bifunctional compound, and when used, a precursor prepolymer having a crosslinkable functional group in the main chain is obtained. Both (Y-1-1) and (Y-1-2) may be used, in which case a prepolymer having a crosslinkable functional group in the main chain and side chain is obtained.
In addition, you may generate | occur | produce the phenolic hydroxyl group in a compound (Y-1) in a reaction system. Specifically, a protected phenolic hydroxyl group that undergoes hydrolysis in the presence of an alkali to become a phenolic hydroxyl group is considered to be the same as the phenolic hydroxyl group. More specifically, a compound such as an ester that gives a phenolic hydroxyl group in the presence of a dehydrofluorinating agent is also included in (Y-1).
As described above, the prepolymer of the present invention preferably has a crosslinkable functional group only in the side chain, and therefore it is more preferable to use only (Y-1-1).
The number of crosslinkable functional groups in each of (Y-1-1) and (Y-1-2) is preferably 1.

Specific examples of the compound (Y-1-1) include phenols having a reactive double bond such as 4-hydroxystyrene, 3-ethynylphenol, 4-phenylethynylphenol, 4- (4-fluorophenyl) ethynyl. Examples include ethynylphenols such as phenol. Specific examples of the compound in which the phenolic hydroxyl group is protected include 4-acetoxystyrene. These may be used alone or in combination of two or more. An aromatic compound having a vinyl group or an ethynyl group as the crosslinkable functional group is preferable, and an aromatic compound having a vinyl group is more preferable.
Note that 4- (4-fluorophenyl) ethynylphenol has an aromatic ring in which one hydrogen atom bonded to the aromatic ring is substituted with a fluorine atom, and this fluorine atom is substantially phenolic. Does not react with hydroxyl groups. Thus, even if it is a compound which the fluorine atom couple | bonded with the aromatic ring, what this fluorine atom does not react with a phenolic hydroxyl group is contained in a compound (Y-1-1).

  Specific examples of the compound (Y-1-2) include 2,2′-bis (phenylethynyl) -5,5′-dihydroxybiphenyl, 2,2′-bis (phenylethynyl) -4,4′-dihydroxy. Examples thereof include bis (phenylethynyl) dihydroxybiphenyls such as biphenyl, and dihydroxydiphenylacetylenes such as 4,4′-dihydroxytolane and 3,3′-dihydroxytolane. These may be used alone or in combination of two or more.

[Compound (Y-2)]
The compound (Y-2) has a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”. Compound (Y-2) does not have a phenolic hydroxyl group.
In the compound (Y-2), the “aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group” preferably has two or more hydrogen atoms bonded to the aromatic ring substituted with a fluorine atom. A perfluoroaromatic ring that is an aromatic ring and in which all of the hydrogen atoms are substituted with fluorine atoms is more preferred. Examples of the perfluoroaromatic ring include perfluorophenyl and perfluorobiphenyl.
When the number of “fluorine atoms capable of reacting with phenolic hydroxyl groups” in (Y-2) is one, (Y-2) works as a monofunctional compound, and in the case of two, it works as a bifunctional compound. In any case, a prepolymer having a crosslinkable functional group introduced in the side chain is obtained.
The number of crosslinkable functional groups in (Y-2) is preferably 1.

Specific examples of the compound (Y-2) include pentafluorostyrene, pentafluorobenzyl acrylate, pentafluorobenzyl methacrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate, perfluorostyrene, pentafluorophenyl trifluorovinyl ether, 3- (penta Fluorinated aryls having a reactive double bond such as fluorophenyl) pentafluoro-1-propene; fluorinated aryls having a cyano group such as pentafluorobenzonitrile; containing fluorinated aryls such as pentafluorophenylacetylene and nonafluorobiphenylacetylene Fluorinated arylacetylenes; fluorinated diaries such as phenylethynylpentafluorobenzene, phenylethynylnonafluorobiphenyl, decafluorotolane, etc. Le acetylenes, and the like.
These may be used alone or in admixture of two or more. Since the crosslinking reaction proceeds at a relatively low temperature and the resulting prepolymer cured product has high heat resistance, the compound (Y-2) includes fluorine-containing arylacetylenes such as pentafluorophenylacetylene, pentafluorostyrene. Fluorine-containing aryls having a reactive double bond such as

[Dehydrofluorinating agent]
As the dehydrofluorinating agent (dehydrating agent) used for producing the precursor (P1) and the precursor (P2), a basic compound is preferable, and in particular, an alkali metal carbonate, hydrogencarbonate or hydroxide. Things are preferred. Specific examples include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like. As a dehydrofluorinating agent used when manufacturing a precursor (P1) and a precursor (P2), sodium carbonate or potassium carbonate is more preferable.

  The amount of the de-HF agent used is required to be 1 or more times in terms of molar ratio with respect to the number of moles of the phenolic hydroxyl group to be reacted, and is preferably 1.1 to 3 times. In other words, the amount of the hydroxyl group of the compound (C) having a phenolic hydroxyl group or the total amount of the hydroxyl groups of the compound (C) and the compound (Y-1) must be 1 or more times in molar ratio. 1.1 to 3 times is preferable.

  The condensation reaction is preferably performed in a polar solvent. As the polar solvent, a solvent containing an aprotic polar solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and the like is preferable. The polar solvent may contain toluene, xylene, benzene, tetrahydrofuran, benzotrifluoride, xylene hexafluoride and the like as long as the solubility of the prepolymer to be produced is not lowered and the condensation reaction is not adversely affected. . By containing these, the polarity (dielectric constant) of the solvent changes, and the reaction rate can be controlled.

  The condensation reaction conditions are preferably 10 to 200 ° C. and 1 to 80 hours. More preferably, it is 2 to 60 hours at 20 to 180 ° C, and most preferably 3 to 48 hours at 50 to 160 ° C.

The number average molecular weight of the prepolymer is in the range of 1 × 10 ^{3 to} 5 × 10 ⁵ , preferably 1.5 × 10 ³ to 1 × 10 ⁵ . Within this range, the coating properties of the coating composition containing the prepolymer of the present invention will be good, and the resulting cured film will have good heat resistance, mechanical properties, solvent resistance, and the like.
In the use of an insulating film for an electronic device, a characteristic (so-called embedding flatness) that sufficiently penetrates between minute spaces of a base and smoothes the surface is required, and the number average molecular weight of the prepolymer is 1.5 × 10. range of ³ to 5 × 10 ⁴ being most preferred.

  In the production method using the compound (Y-1), the number average molecular weight of the prepolymer is the sum of the compound (C), the compound (Y-1) and the alcohol (Q), and the fluorine-containing aromatic compound (B). It can be controlled by changing the charging ratio. Here, it is preferable that no hydroxyl group remains in the prepolymer because the water repellency and oil repellency are improved.

  In the condensation reaction, the fluorine-containing aromatic compound (B) usually serves as a bifunctional compound. Therefore, the molecular weight is controlled in such a range that the total number of moles of hydroxyl groups of the compound (C), the compound (Y-1), and the alcohol (Q) does not exceed twice the number of moles of the fluorinated aromatic compound (B). It is preferable to adjust within.

  The number average molecular weight of the prepolymer in the production method using the compound (Y-2) is the sum of the fluorine-containing aromatic compound (B) and the compound (Y-2) and the sum of the compound (C) and the alcohol (Q). It can be controlled by changing the charging ratio. Here, similarly to the above, when the compound (Y-2) works as a monofunctional compound, the total number of moles of the hydroxyl group is twice the number of moles of the fluorine-containing aromatic compound (B) and the compound ( It is preferable to adjust within a range not exceeding the total number of moles of Y-2). When the compound (Y-2) functions as a bifunctional compound, the total number of moles of hydroxyl groups does not exceed twice the total number of moles of the fluorine-containing aromatic compound (B) and the compound (Y-2). It is preferable to adjust within.

  Moreover, in the manufacturing method using a compound (Y-2), when the reaction rates of a fluorine-containing aromatic compound (B) and a compound (Y-2) differ, the molecular weight and composition of the precursor or prepolymer obtained by an addition order are different. May be different. For example, when the reaction rate for the phenoxy group derived from the phenolic hydroxyl group of the compound (C) is (B)> (Y-2), the fluorine-containing aromatic compound (B) and the compound (Y-2) When charged at the same time, before all the compound (Y-2) is consumed, all the phenoxy groups may be consumed by the fluorine-containing aromatic compound (B), and the unreacted compound (Y-2) may remain. . In such a case, in order to increase the reaction rate of the compound (Y-2), it is preferable to charge the fluorine-containing aromatic compound (B) after first charging the compound (Y-2). However, in this method, the variation of the composition between the molecular chains of the obtained precursor tends to be large. When it is necessary to reduce the variation in the composition between the molecular chains of the obtained precursor, it is preferable to manufacture by batch preparation.

In the production method using the compound (Y-1), the amount of the compound (C) used is preferably 0.1 to 1 time, more preferably 0.3 to 0.00, in terms of the molar ratio to the fluorine-containing aromatic compound (B). It is 6 times, and the amount of the compound (Y-1) used is preferably 0.1 to 2 times, more preferably 0.2 to 1.5 times in terms of a molar ratio to the fluorine-containing aromatic compound (B).
In the production method using the compound (Y-2), the amount of the compound (C) used is preferably 0.5 to 2 times, more preferably 0.6 to 1 in terms of the molar ratio to the fluorine-containing aromatic compound (B). It is 5 times, and the usage-amount of a compound (Y-2) is 0.1-2 times by molar ratio with respect to a fluorine-containing aromatic compound (B), More preferably, it is 0.2-1.5 times. When each value is in this range, the obtained prepolymer of the present invention has high heat resistance, which is preferable.

  The prepolymer of the present invention has the desired physical properties by appropriately selecting the compounds (Y-1) and (Y-2) according to the physical properties such as heat resistance and flexibility of the cured product obtained by curing the prepolymer. A prepolymer from which a cured product of the above can be obtained can be produced.

  The prepolymer of the present invention is subjected to neutralization, reprecipitation, after a condensation reaction in the intermediate step (for example, after synthesizing a precursor or after introducing a side chain represented by the general formula (I)), It is preferable to perform purification appropriately by a method such as extraction or filtration.

[Other co-condensation components]
In a cured product produced using a prepolymer, if the heat resistance is insufficient or the film or film made of the cured product is brittle, the heat resistance of the cured product is improved and the flexibility is improved. Therefore, other cocondensation components other than the above (B) (C) (Y-1) (Y-2) (Q) can be added during the production of the prepolymer.
Examples of the other cocondensation component include a compound (Z) having two phenolic hydroxyl groups other than (Y-1) for improving the flexibility of the cured film.

  Examples of the compound (Z) having two phenolic hydroxyl groups include dihydroxybenzene, dihydroxybiphenyl, dihydroxyterphenyl, dihydroxynaphthalene, dihydroxyanthracene, dihydroxyphenanthracene, dihydroxy-9,9-diphenylfluorene, dihydroxydibenzofuran, dihydroxydiphenyl ether. And bifunctional phenols such as dihydroxydiphenyl thioether, dihydroxybenzophenone, dihydroxy-2,2-diphenylpropane, dihydroxy-2,2-diphenylhexafluoropropane, and dihydroxybinaphthyl. These may be used alone or in combination of two or more.

[Alcohol (Q)]
In the present invention, in order to introduce the side chain represented by the general formula (I), the alcohol (Q) represented by the general formula (II) is preferably used. In particular, it is preferable to react the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” and the alcohol (Q) in the presence of a dehydrofluorinating agent.
The reaction between the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” and the alcohol (Q) is derived from the hydroxyl group of the alcohol (Q), similarly to the reaction represented by the formula (2). The alkoxy group is attacked by the carbon atom to which the halogen atom of the “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” is bonded, and then the ether bond is formed by the reaction mechanism etc. Generate.
By this reaction, a side chain obtained by removing hydrogen from the hydroxyl group of alcohol (Q), that is, a side chain represented by the general formula (I) is introduced into the prepolymer.

^{R f} in the general formula (II) is the same as ^{R f} in the general formula (I). Specific examples of the alcohol (Q) represented by the general formula (II) include the following.
When an alcohol represented by the following general formula (II-1) is used, a prepolymer having a side chain represented by the above general formula (I-1) can be obtained. A prepolymer having side chains is obtained. The alcohol (Q) may be used alone or in combination of two or more.
Of the alcohols (Q) represented by the general formula (II), the linear ones are preferably those represented by the following general formula (II-1) or the following general formula (II-2). In the following general formula (II-1), m represents an integer of 1 to 5, R ^fa represents a fluorine-containing alkyl group having 4 to 50 carbon atoms, and may contain an etheric oxygen atom. m is more preferably an integer of 1 to 3.
More preferable examples of the alcohol (Q) represented by the following general formula (II-1) include an alcohol represented by the following general formula (II-1-1) or the following general formula (II-1-2). The alcohol represented is mentioned.

  Moreover, as a branched thing among alcohol (Q) represented by the said general formula (II), the alcohol represented by the following general formula (II-3) or (II-4) is preferable.

  Moreover, as a cyclic thing among alcohol (Q) represented by the said general formula (II), the alcohol represented by the following formula (II-5), (II-6), or (II-7) is preferable.

As the dehydrofluorinating agent used when reacting the alcohol (Q), the same deHF agent used for the condensation reaction of the compound (B), the compound (C) and the compound (Y) can be used. That is, the deHF agent is preferably a basic compound, and particularly preferably an alkali metal hydride, carbonate, bicarbonate or hydroxide. Specific examples include sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, cesium hydroxide and the like. As the dehydrofluorinating agent used in the production of reacting the alcohol (Q), sodium hydride, cesium carbonate, sodium hydroxide, potassium hydroxide or cesium hydroxide is more preferable.
The amount of the deHF agent to be used is required to be 1 or more times in terms of molar ratio with respect to the number of moles of the hydroxyl group of the alcohol (Q) to be used, and preferably 1.1 to 3 times.
When reacting alcohol (Q), it is preferable to carry out in a polar solvent. Examples of polar solvents include ethereal solvents such as tetrahydrofuran and 1,4-dioxane, aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane. The solvent to contain is preferable.
The reaction conditions are preferably 0 to 200 ° C. and 1 to 80 hours. More preferably, it is 2 to 60 hours at 20 to 180 ° C, and most preferably 3 to 48 hours at 30 to 100 ° C.

<Hardened product>
When external energy is applied to the prepolymer of the present invention, the crosslinkable functional group reacts to cause crosslinking or chain extension between the crosslinked prepolymer molecules, resulting in a cured product. The shape of the cured product is not particularly limited. For example, it is a film, a film, a molded body, or the like.
In particular, when a liquid coating composition containing the prepolymer of the present invention and a solvent is prepared, the coating composition is coated on a substrate, cured and formed into a film shape, the reaction of the crosslinkable functional group occurs. A uniform cured product (cured film) can be obtained which is easy to proceed uniformly. Therefore, the prepolymer of the present invention is suitable for producing a cured film.
<Coating composition>
The coating composition of the present invention contains the prepolymer of the present invention and a solvent. The coating composition containing the prepolymer of the present invention is obtained by dissolving or dispersing the prepolymer in a solvent. The coating composition of this invention is used suitably for manufacture of a cured film or a cured film. The coating composition of the present invention may contain other components as necessary.

<Solvent>
The solvent in the coating composition of the present invention may be any solvent that can dissolve or disperse the prepolymer and additives added as necessary. In addition, the coating composition of the present invention is formed by a desired method to form a coating film having a desired film thickness, good film thickness uniformity, and embedded flatness as required. It is preferable to use a solvent suitable for achieving the properties.
Examples of the solvent include aromatic hydrocarbons, dipolar aprotic solvents, ketones, esters, ethers, and halogenated hydrocarbons. The solvent may be the same as or different from the reaction solvent used in the production of the prepolymer described above. When using a different solvent, the prepolymer is once recovered from the reaction solution by a reprecipitation method or the like and dissolved or dispersed in a different solvent, or a known method such as an evaporation method or an ultrafiltration method is used. Thus, solvent replacement can be performed.

Aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, tetralin, methylnaphthalene and the like. Examples of the dipole aprotic solvents include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide and the like.
Examples of ketones include cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methyl amyl ketone, and the like. Examples of ethers include tetrahydrofuran, pyran, dioxane, dimethoxyethane, diethoxyethane, diphenyl ether, anisole, phenetole, diglyme, and triglyme.
Esters include ethyl lactate, methyl benzoate, ethyl benzoate, butyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether Propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate and the like.
Examples of halogenated hydrocarbons include carbon tetrachloride, chloroform, methylene chloride, tetrachloroethylene, chlorobenzene, dichlorobenzene and the like.

  The amount of the solvent used is preferably adjusted so that the solid content concentration of the prepolymer in the coating composition of the present invention is 1 to 50% by mass, more preferably 5 to 40% by mass.

<Other ingredients>
It is preferable to add various catalysts or additives to the photosensitive composition of the present invention for the purpose of increasing the reaction rate when curing the prepolymer or reducing reaction defects.
For example, when the prepolymer contains an ethynyl group as a crosslinkable functional group, the catalyst contains amines such as aniline, triethylamine, aminophenyltrialkoxysilane, aminopropyltrialkoxysilane, molybdenum, nickel, etc. Organometallic compounds are preferred.
As the additive, a biscyclopentadienone derivative is preferable. An ethynyl group and a cyclopentadienone group (1-oxocyclopenta-2,5-dien-3-yl group) form an adduct by Diels-Alder reaction with heat, and then decarbonize to form an aromatic ring. Form. Therefore, when a biscyclopentadienone derivative is used, a bridge or chain extension in which an aromatic ring is a binding site is formed.

Specific examples of the biscyclopentadienone derivative include 1,4-bis (1-oxo-2,4,5-triphenyl-cyclopenta-2,5-dien-3-yl) benzene, 4,4′- Bis (1-oxo-2,4,5-triphenyl-cyclopenta-2,5-dien-3-yl) biphenyl, 4,4′-bis (1-oxo-2,4,5-triphenyl-cyclopenta -2,5-dien-3-yl) 1,1'-oxybisbenzene, 4,4'-bis (1-oxo-2,4,5-triphenyl-cyclopenta-2,5-diene-3- Yl) 1,1′-thiobisbenzene, 1,4-bis (1-oxo-2,5-di- [4-fluorophenyl] -4-phenyl-cyclopenta-2,5-dien-3-yl) Benzene, 4,4′-bis (1-oxo-2,4,5-tri Enyl-cyclopenta-2,5-dien-3-yl) 1,1 ′-(1,2-ethanediyl) bisbenzene, 4,4′-bis (1-oxo-2,4,5-triphenyl-cyclopenta -2,5-dien-3-yl) 1,1 '-(1,3-propanediyl) bisbenzene and the like.
Among these biscyclopentadienone derivatives, biscyclopentadienone derivatives having a wholly aromatic skeleton are preferable from the viewpoint of heat resistance. These may be used alone or in combination of two or more.

  In the coating composition of the present invention, in addition to the catalyst and / or additive, stabilizers such as an ultraviolet absorber, an antioxidant, and a thermal polymerization inhibitor; a leveling agent, an antifoaming agent, a suspending agent, and a dispersant At least one additive selected from various additives well known in the coating field such as a surfactant, a crosslinking agent, a plasticizer, and a thickener may be blended. Moreover, when forming the film | membrane or film which has a void | hole, the substance etc. which can be removed after hollow body mentioned later and thin film formation can be mix | blended suitably.

<Curing film>
About the manufacturing method of hardened | cured material, a cured film is mentioned as a suitable example of hardened | cured material.
The coating composition of the present invention is applied to a suitable substrate surface to form a wet film, and then the solvent is removed by volatilization or the like, or after the removal, a curing treatment is performed to form a crosslinkable functional group in the prepolymer. A cured film can be formed by causing a crosslinking reaction.
As a method for forming the wet film, it is preferable to employ a coating method or a printing method. Examples of the coating method include known coating methods such as spin coating, dip coating, spray coating, die coating, bar coating, doctor coating, extrusion coating, scan coating, brush coating, and potting. Is mentioned. Examples of the printing method include nanoimprinting, screen printing, gravure printing, and ink jet printing.

  In addition, when the prepolymer contains a low molecular weight substance having a substantial vapor pressure at room temperature, in order to prevent volatilization at the time of baking, before applying the coating composition, the crosslinkable functional group in solution. A part of the group can be allowed to react. The method is preferably heating. As heating conditions, 1 to 50 hours are preferable at 50 ° C to 250 ° C, and more preferably 1 to 20 hours at 70 to 200 ° C. The reaction rate of the crosslinkable functional group in the solution is preferably less than 50%, more preferably less than 30%, from the viewpoint of preventing gelation of the prepolymer in the solution.

  The thickness of the wet film formed by the coating composition can be appropriately set according to the shape of the cured film to be produced. For example, for the purpose of producing a film, it is preferable to form a wet film of about 0.01 to 500 μm on the substrate, more preferably 0.1 to 300 μm.

In the curing process, the crosslinkable functional group provides external energy that causes a reaction. Such external energy is selected according to the kind of the crosslinkable functional group present in the prepolymer. Preferably, a crosslinkable functional group that reacts by heat is used, and the curing treatment is performed by baking (heating). The heating condition is preferably about 150 to 450 ° C. for about 1 to 120 minutes, and more preferably about 160 to 350 ° C. for about 2 to 60 minutes. As the heating device, a hot plate, an oven, and a furnace (furnace) are preferable, and examples of the heating atmosphere include an inert gas atmosphere such as nitrogen or argon, air, oxygen, and reduced pressure. An inert gas atmosphere and reduced pressure are preferred. In order to ensure the surface smoothness of the thin film or improve the fine space embedding property of the thin film, a pre-baking process of about 50 to 250 ° C. is added or the heating process is performed in several stages. Is preferred.
As for the reaction rate of a crosslinkable functional group in the cured film obtained after a hardening process, 30-100 mol% is preferable. By setting the reaction rate to 30 mol% or more, the heat resistance and chemical resistance of the cured film are improved. In this respect, the reaction rate is more preferably 50 mol% or more, and most preferably 70 mol% or more.

  The cured film obtained from the coating composition of the present invention can be peeled off from the substrate and used as a single film, or used as a coating such as a water- and oil-repellent film while still adhered to the substrate. You can also. In the latter case, an adhesion promoter (adhesion improver) can be used to improve the adhesion between the cured film and the substrate.

Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents and the like. Silane coupling agents such as vinyl silanes, acrylic silanes, styryl silanes, epoxy silanes, and amino silanes are more preferable.
Examples of vinyl silanes include vinyl trichlorosilane, vinyl trimethoxy silane, and vinyl triethoxy silane. Examples of styrylsilanes include p-styryltrimethoxysilane and p-styryltriethoxysilane.
As acrylic silanes, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Examples include silane.
As epoxy silanes, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Is exemplified.
Examples of aminosilanes include aliphatic aminosilanes such as 3-aminopropylmethyldiethoxysilane and 3-aminopropyltriethoxysilane, aminophenyltrimethoxysilane, aminophenyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxy. Aromatic group aminosilanes such as silane can be mentioned.
As a method for applying the adhesion promoter, a method of treating the substrate with the adhesion promoter before application of the coating composition or a method of adding the adhesion promoter to the coating composition is preferable. As a method for treating the substrate with an adhesion promoter, in the case of aminosilanes, a method of spin-coating the substrate as a 0.01 to 3 mass% alcohol-based solution can be mentioned. As alcohol, methanol, ethanol, and isopropyl alcohol are preferable. In the method of adding the adhesion promoter to the prepolymer solution, the addition amount of the adhesion promoter is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass with respect to the prepolymer contained. If the addition amount of the adhesion promoter is small, the effect of improving the adhesiveness is not sufficient, and if it is too much, the heat resistance is lowered.

<Use of cured product>
According to the present invention, a prepolymer having a polyaryl ether structure in the main chain, a crosslinkable functional group, and a specific side chain represented by the above general formula (I) is obtained, and the prepolymer is cured. In the cured product, good heat resistance, high water repellency, and high oil repellency can be achieved at the same time.

The cured product or cured film produced using the prepolymer of the present invention is suitable for applications requiring heat resistance, water repellency and oil repellency.
Specific examples of applications include molds, mold release materials (particularly for forming fine patterns such as hot embossing and nanoimprint lithography); surfaces for MEMS (microelectronic mechanical systems) devices such as inkjet printer heads and sensors. Protective film; Copier fixing roll coating; Liquid lens member coating; Oil sealant; Bonding member or sealant coating; Automotive injector coating; Oil repellent waterproof breathable filter; Sealant; Bank material; Additives; Water and oil repellent films for household appliances and cooking utensils; Weather-resistant coatings; Moisture-proof coatings; Various protective films (heat and water repellent films, heat and oil repellent films); Various films (heat and water repellent films, heat resistant) -Oil repellent film);

In particular, the prepolymer introduced with the side chain represented by the above general formula (I) has heat resistance, water repellency, oil repellency, non-adhesion, low friction, friction resistance, low dielectric constant, and low Since a cured product or a cured film satisfying the birefringence can be formed, it is suitable for the above-mentioned use and widely applicable to other uses.
Specific examples of uses of the cured product or cured film of the prepolymer of the present invention include various battery membrane materials such as fuel cells; automotive engine pistons, copier fixing unit bearings, air conditioner compressor bearings, automotive engine bearings, cars Coatings for compressor swash plates, automotive sliding bearings, etc .; heat-sink insulating coatings for power semiconductors; insulating films for electronic devices or multilayer wiring boards; electronic components; LCD alignment films; optical waveguides; It is done.

<Article>
The article having the cured film of the present invention is not particularly limited, but preferred examples include molds, molds (particularly for forming fine patterns such as hot embossing and nanoimprint lithography), inkjet printer heads, sensors, etc. MEMS (microelectronic mechanical system) devices; photocopier fixing rolls; liquid lens members; oil seal materials; joint members or seal materials; automobile injectors; oil repellent waterproof breathable filters; sealants; bank materials; Water and oil repellent members for equipment; weather resistant coating; moisture proof coating; various protective films (heat and water repellent film, heat and oil repellent film); various films (heat and water repellent film, heat and oil repellent film); Various battery membrane materials such as fuel cells; Automotive engine pistons; Copier fixing unit bearings Compressor bearings for air conditioners; automotive engine bearings; car compressor swash plates; sliding bearings for automobiles; heat-sink insulating coatings for power semiconductors; insulating films for electronic devices or multilayer wiring boards; electronic components; LCD alignment films; Non-linear optical material;

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Each measurement item was measured by the following method.

[Molecular weight]
The number average molecular weight in terms of polystyrene was determined from the vacuum-dried prepolymer powder by gel permeation chromatography (GPC method). Tetrahydrofuran was used as the carrier solvent.
[Confirmation of ether bond]
The vacuum-dried prepolymer powder was measured by IR and confirmed by absorption near 1300 cm ⁻¹ .
[Confirmation of crosslinkable functional groups]
The vacuum-dried prepolymer powder was dissolved in heavy acetone, and NMR was measured to confirm that there was a signal in a predetermined region. When the crosslinkable functional group is a vinyl group, a signal appears at δ = 5.0 to 7.0 ppm, and when the crosslinkable functional group is an ethynyl group, a signal appears near δ = 4.5 ppm.

[Synthesis Example 1: Synthesis of Precursor (P2-1)]
A precursor (P2-1) was produced by the production method (ii) using the compounds (B), (C), and (Y-2).
That is, 1.15 g (0.006 mol) of pentafluorophenylacetylene as compound (Y-2) and 1,3,5-as compound (C) in a 50 mL two-necked flask equipped with a Dimroth condenser and a stirrer chip. 0.65 g of trihydroxybenzene (0.005 mol), 2.00 g (0.006 mol) of perfluorobiphenyl as the compound (B), and 34.22 g of DMAc (N, N-dimethylacetamide) as the solvent. Prepared.
While stirring, the mixture was heated to 60 ° C. on an oil bath, 3.23 g (0.03 mol) of sodium carbonate was quickly added as a de-HF agent, and heated at 60 ° C. for 22 hours while stirring was continued.
Thereafter, the reaction solution was cooled to room temperature and gradually poured into 150 mL of vigorously stirred 0.5N aqueous hydrochloric acid, whereby a fine brown powder was precipitated. This fine brown powder was filtered and further washed twice with pure water, followed by vacuum drying at 80 ° C. for 12 hours to obtain 2.58 g of a white gray powder precursor (P2-1). .

[Synthesis Example 2: Synthesis of Precursor (P2-2)]
Using the compounds (B), (C) and (Y-2), a precursor (P2-2) was produced by the production method (ii).
Into a 100 mL glass four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer, 2.2 g (0.01 mol) of pentafluorostyrene as compound (Y-2), 1, as compound (C) 3.3 g (0.01 mol) of 1,1-tris (4-hydroxyphenyl) ethane and 49.2 g of DMAc as a solvent were charged.
While stirring, the mixture was heated on an oil bath, and when the liquid temperature reached 60 ° C., 5.1 g (0.05 mol) of sodium carbonate was quickly added as a deHF agent. The mixture was heated at 60 ° C. for 24 hours while stirring was continued.
Next, a solution of 4.0 g (0.01 mol) of perfluorobiphenyl as compound (B) in 36.0 g of DMAc was added, and the mixture was further heated at 60 ° C. for 17 hours.
Thereafter, the reaction solution was cooled to room temperature and gradually added dropwise to about 300 mL of vigorously stirred 0.5N aqueous hydrochloric acid for reprecipitation. After filtration, and further washed twice with pure water, vacuum drying was performed at 60 ° C. for 12 hours to obtain 7.5 g of a white powder precursor (P2-2).
[Synthesis Example 3: Synthesis of Precursor (P1-1)]
A precursor (P1-1) was produced using the compounds (B) and (C).
That is, in a 200 mL two-necked flask equipped with a Dimroth condenser and a stirrer chip, 1.79 g (0.014 mol) of 1,3,5-trihydroxybenzene as compound (C) and perfluorobiphenyl as compound (B) Was charged with 10.0 g (0.030 mol) and 106.14 g of DMAc as the solvent.
While stirring, the mixture was heated to 40 ° C. on an oil bath, 8.84 g (0.064 mol) of potassium carbonate was quickly added as a de-HF agent, and heated at 40 ° C. for 24 hours while continuing stirring.
Thereafter, the reaction liquid was cooled to room temperature and gradually poured into 300 mL of vigorously stirred 0.5N aqueous hydrochloric acid to precipitate a white powder. This white powder was filtered, further washed twice with pure water, and then vacuum dried at 80 ° C. for 12 hours to obtain 9.84 g of a white powder precursor (P1-1).

[Example 1: Introduction of side chain to precursor (P2-1)]
A 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer was charged with 3 g of the precursor (P2-1) obtained in Synthesis Example 1 and CF ₃ ( 0.45 g (0.0004 mol) of OCF ₂ CF ₂ ) _n OCF ₂ CH ₂ OH (average molecular weight 1000) (Q-1) and 31.1 g of tetrahydrofuran (THF) as a solvent were charged.
While stirring at room temperature, 0.06 g (0.001 mol) of sodium hydride (55% mineral oil dispersion) was added as a deHF agent. After the addition, the mixture was heated to 30 ° C. on an oil bath while stirring and stirred for 45 hours.
Thereafter, the reaction solution was cooled to room temperature and gradually added to 120 g of hydrochloric acid water-containing methanol (mixed solution of 6 g of hydrochloric acid and 114 g of methanol) to precipitate a fine brown powder. This fine brown powder was filtered, further washed with methanol three times, then with hexane three times, and vacuum dried at 60 ° C. for 12 hours to obtain 2.4 g of a white gray powdery prepolymer A. It was.

The NMR spectrum data of the prepolymer A obtained in this example is shown below. The NMR spectrum data is shown as an apparent chemical shift range (hereinafter the same). Hereinafter, tetramethylsilane is referred to as TMS.
<NMR spectrum>
¹ H-NMR (300.4 MHz, solvent acetone-d6, standard: TMS) δ (ppm): 4.50 (CC-H), 5.08 (CF ₂ —CH ₂ —O), 6.69-7 .24 (Ph-H).
¹⁹ F-NMR (282.7 MHz, solvent acetone-d6, reference: CFCl ₃ ) δ (ppm): −55.2 (CF ₃ ), −77.9 (—CF ₂ —CH ₂ O), −88. _{2~-90.3 (CF 2 -O)} , - 137.2~-161.9 (Ph-F).

[Example 2: Introduction of side chain to precursor (P2-2)]
In the same four-necked flask as in Example 1, 3 g of the precursor (P2-2) obtained in Synthesis Example 2 and 0.45 g (0.0004 mol) of the same alcohol (Q-1) as in Example 1 were used. 32.2 g of the same solvent (THF) as in Example 1 was charged.
While stirring at room temperature, 0.06 g (0.001 mol) of the same deHF agent as in Example 1 was added. After the addition, the mixture was heated to 50 ° C. on an oil bath while stirring and stirred for 24 hours.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 1 was performed to obtain 2.8 g of a white gray powdery prepolymer B.

The NMR spectrum data of the prepolymer B obtained in this example is shown below.
<NMR spectrum>
¹ H-NMR (300.4 MHz, solvent acetone-d6, standard: TMS) δ (ppm): 2.19 (C—CH ₃ ), 5.08 (CF ₂ —CH ₂ —O), 5.77 ( _{Ph-CH = CH 2),} 6.08 (Ph-CH = CH 2), 6.73 (Ph-CH = CH 2), 6.90~7.21 (Ph-H).
¹⁹ F-NMR (282.7 MHz, solvent acetone-d6, reference: CFCl ₃ ) δ (ppm): −55.2 (CF ₃ ), −77.9 (—CF ₂ —CH ₂ O), −88. _{2~-90.3 (CF 2 -O)} , - 138.3~-161.9 (Ph-F).

[Example 3: Introduction of side chain to precursor (P2-2)]
In a four-necked flask similar to Example 1 above, 3 g of the precursor (P2-2) obtained in Synthesis Example 2 and CF ₃ CF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CH ₂ as alcohol (Q) were used. 0.75 g (0.002 mol) of OH (Q-2) and 33.8 g of the same solvent as in Example 1 were charged.
While stirring at room temperature, 0.23 g (0.005 mol) of the same deHF agent as in Example 1 was added. After the addition, the mixture was heated to 50 ° C. on an oil bath while stirring and stirred for 94 hours.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 1 was performed to obtain 3.1 g of a white gray powdery prepolymer C.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Example 4: Side chain introduction into precursor (P2-2)]
In the same four-necked flask as in Example 1 above, 2.5 g of the precursor (P2-2) obtained in Synthesis Example 2, and CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ OCF ₂ as the alcohol (Q). 0.63 g (0.001 mol) of CF ₂ OCF ₂ CH ₂ OH (Q-3) and 28.1 g of the same solvent as in Example 1 were charged.
While stirring at room temperature, 0.16 g (0.004 mol) of the same deHF agent as in Example 1 was added. After the addition, the mixture was heated to 50 ° C. on an oil bath while stirring and stirred for 69 hours.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 1 was performed to obtain 2.5 g of a white gray powdery prepolymer D.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Example 5: Side chain introduction to precursor (P2-2)]
In the same four-necked flask as in Example 1 above, 3.0 g of the precursor (P2-2) obtained in Synthesis Example 2 and CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF as alcohol (Q) 0.75 g (0.002 mol) of (CF ₃ ) CH ₂ OH (Q-4) and 33.8 g of the same solvent as in Example 1 were charged.
While stirring at room temperature, 0.20 g (0.005 mol) of the same deHF agent as in Example 1 was added. After the addition, the mixture was heated to 50 ° C. on an oil bath while stirring and stirred for 17 hours.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 1 was performed to obtain 3.1 g of a white gray powdery prepolymer E.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Example 6: Side chain introduction into precursor (P2-2)]
In a four-necked flask similar to Example 1 above, 2.0 g of the precursor (P2-2) obtained in Synthesis Example 2 and FAdCH ₂ OH (Q-5) represented by the following chemical formula as alcohol (Q) Of 0.50 g (0.001 mol) and 22.5 g of the same solvent as in Example 1 were charged.
While stirring at room temperature, 0.15 g (0.003 mol) of the same deHF agent as in Example 1 was added. After the addition, the mixture was heated to 50 ° C. on an oil bath while stirring and stirred for 45 hours.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 1 was performed to obtain 1.9 g of white polymer powdered prepolymer F.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Example 7: Introduction of side chain to precursor (P1-1)]
Into a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer, 3 g of the precursor (P1-1) obtained in Synthesis Example 3, the same alcohol (Q -1) of 0.75 g (0.0007 mol) and 33.8 g of DMAc as a solvent were charged.
While stirring, the mixture was heated to 60 ° C. on an oil bath, 0.94 g (0.003 mol) of cesium carbonate was quickly added as a deHF agent, and heated at 60 ° C. for 46 hours while stirring was continued.
Thereafter, the reaction solution was cooled to room temperature and gradually added to 120 g of vigorously stirred 0.5 mol / L hydrochloric acid to precipitate a white gray powder. The white gray powder was filtered, washed with water three times, and then vacuum-dried at 60 ° C. for 12 hours to obtain 3.1 g of a white gray powder polymer.
Subsequently, 2 g of the polymer obtained by the above reaction and a phenolic hydroxyl group were protected in a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer (Y-1). Was charged with 0.35 g (0.002 mol) of 4-acetoxystyrene and 21.2 g of diethylene glycol dimethyl ether as a solvent.
While stirring, 0.76 g (0.006 mol) of potassium hydroxide (48% aqueous solution) was quickly added and stirred for 22 hours.
Thereafter, when the reaction solution was gradually added to 100 g of 0.5 mol / L hydrochloric acid vigorously stirred, a white gray powder was precipitated. The white gray powder was filtered, further washed with water three times, and then vacuum dried at 60 ° C. for 12 hours to obtain 2.0 g of a white gray powdery prepolymer G.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Example 8: Introduction of side chain to precursor (P1-1)]
Into a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer, 3 g of the precursor (P1-1) obtained in Synthesis Example 3, the same alcohol (Q -1) 0.45 g (0.0004 mol) and 31.1 g of DMAc as a solvent were charged.
While stirring, the mixture was heated to 60 ° C. on an oil bath, 0.56 g (0.002 mol) of cesium carbonate was quickly added as a deHF agent, and heated at 60 ° C. for 41 hours while stirring was continued.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 7 was performed to obtain 2.8 g of a white gray powdery polymer.
Subsequently, a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer was charged with 2.5 g of the polymer obtained by the above reaction and 0.50 g (0 of 4-acetoxystyrene). 0.003 mol) and 27.1 g of diethylene glycol dimethyl ether as a solvent were charged.
While stirring, 1.1 g (0.009 mol) of potassium hydroxide (48% aqueous solution) was quickly added and stirred for 25 hours.
Thereafter, the same operation as in Example 7 was performed to obtain 2.5 g of a white gray powdery prepolymer H.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Example 9: Side chain introduction into precursor (P1-1)]
Into a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer, 3 g of the precursor (P1-1) obtained in Synthesis Example 3, the same alcohol (Q -1) 0.45 g (0.0004 mol) and 31.1 g of DMAc as a solvent were charged.
While stirring, the mixture was heated to 60 ° C. on an oil bath, 0.56 g (0.002 mol) of cesium carbonate was quickly added as a deHF agent, and heated at 60 ° C. for 41 hours while stirring was continued.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 7 was performed to obtain 2.8 g of a white gray powdery polymer.
Subsequently, a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer was charged with 2.5 g of the polymer obtained in the above reaction and 0.38 g of 4-acetoxystyrene (0 0.002 mol) and 25.9 g of diethylene glycol dimethyl ether as a solvent.
While stirring, 0.82 g (0.007 mol) of potassium hydroxide (48% aqueous solution) was quickly added and stirred for 44 hours.
Thereafter, the same operation as in Example 7 was performed to obtain 2.4 g of a prepolymer I in the form of white gray powder.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Example 10: Introduction of side chain to precursor (P1-1)]
Into a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer, 3 g of the precursor (P1-1) obtained in Synthesis Example 3, the same alcohol (Q -1) 0.45 g (0.0004 mol) and 31.1 g of DMAc as a solvent were charged.
While stirring, the mixture was heated to 60 ° C. on an oil bath, 0.56 g (0.002 mol) of cesium carbonate was quickly added as a deHF agent, and heated at 60 ° C. for 41 hours while stirring was continued.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 7 was performed to obtain 2.8 g of a white gray powdery polymer.
Subsequently, a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer was charged with 2.5 g of the polymer obtained in the above reaction and 0.25 g of 4-acetoxystyrene (0 0.002 mol), and 24.8 g of diethylene glycol dimethyl ether was charged as a solvent.
While stirring, 0.55 g (0.005 mol) of potassium hydroxide (48% aqueous solution) was quickly added and stirred for 44 hours.
Thereafter, the same operation as in Example 7 was performed to obtain 2.4 g of a white gray powdery prepolymer J.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Example 11: Introduction of side chain to precursor (P1-1)]
Into a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer, 4 g of the precursor (P1-1) obtained in Synthesis Example 3 and the same alcohol (Q -1) 0.20 g (0.0002 mol) and 37.8 g of DMAc as a solvent were charged.
While stirring, the mixture was heated to 60 ° C. on an oil bath, 0.25 g (0.001 mol) of cesium carbonate was quickly added as a de-HF agent, and heated at 60 ° C. for 46 hours while stirring was continued.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 7 was performed to obtain 3.9 g of a white gray powdery polymer.
Subsequently, a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer was charged with 2 g of the polymer obtained by the above reaction and 0.52 g (0.003 of 4-acetoxystyrene). Mol) and 22.7 g of diethylene glycol dimethyl ether as a solvent.
While stirring, 1.1 g (0.010 mol) of potassium hydroxide (48% aqueous solution) was quickly added and stirred for 22 hours.
Thereafter, the same operation as in Example 7 was performed to obtain 2.1 g of a white gray powdery prepolymer K.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Example 12: Introduction of side chain to precursor (P1-1)]
Into a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer, 4 g of the precursor (P1-1) obtained in Synthesis Example 3 and the same alcohol (Q -1) 0.20 g (0.0002 mol) and 37.8 g of DMAc as a solvent were charged.
While stirring, the mixture was heated to 60 ° C. on an oil bath, 0.25 g (0.001 mol) of cesium carbonate was quickly added as a de-HF agent, and heated at 60 ° C. for 46 hours while stirring was continued.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 7 was performed to obtain 3.9 g of a white gray powdery polymer.
Subsequently, a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer was charged with 3 g of the polymer obtained by the above reaction and 0.57 g (0.004 of 4-acetoxystyrene). Mol), and 32.2 g of diethylene glycol dimethyl ether was charged as a solvent.
While stirring, 1.2 g (0.011 mol) of potassium hydroxide (48% aqueous solution) was quickly added and stirred for 23 hours.
Then, operation similar to Example 7 was performed and the prepolymer L of 2.7g of white gray powder form was obtained.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Example 13: Introduction of side chain to precursor (P1-1)]
Into a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer, 4 g of the precursor (P1-1) obtained in Synthesis Example 3 and the same alcohol (Q -1) 0.20 g (0.0002 mol) and 37.8 g of DMAc as a solvent were charged.
While stirring, the mixture was heated to 60 ° C. on an oil bath, 0.25 g (0.001 mol) of cesium carbonate was quickly added as a de-HF agent, and heated at 60 ° C. for 46 hours while stirring was continued.
Thereafter, the reaction solution was cooled to room temperature, and the same operation as in Example 7 was performed to obtain 3.9 g of a white gray powdery polymer.
Subsequently, a 50 mL Pyrex (registered trademark) four-necked flask equipped with a Dimroth condenser, thermocouple thermometer, and mechanical stirrer was charged with 3 g of the polymer obtained in the above reaction and 0.38 g (0.002) of 4-acetoxystyrene. Mol), and 30.4 g of diethylene glycol dimethyl ether was charged as a solvent.
While stirring, 0.82 g (0.007 mol) of potassium hydroxide (48% aqueous solution) was quickly added and stirred for 24 hours.
Then, operation similar to Example 7 was performed and the prepolymer M of 2.8g of white gray powder form was obtained.
The obtained prepolymer had an ether bond, a vinyl group as a crosslinkable functional group, and a fluorine-containing side chain.

[Contact angle evaluation]
A cured film is formed by using the precursors P2-1 and P2-2 obtained in Synthesis Examples 1 and 2 and the vacuum dried products (resin powders) of the prepolymers A to F obtained in Examples 1 to 6, The contact angle of the cured film was measured by the following method. The measurement results are shown in Table 1. In Table 1, “N / A” means not evaluated.

The vacuum dried product (resin powder) obtained in Synthesis Examples 1 and 2 and Examples 1 to 6 was dissolved in cyclohexanone to give a 15 wt% solution, and this solution was PTFE (tetrafluoroethylene resin having a pore diameter of 0.5 μm). ). The obtained filtrate was applied on a silicon wafer by a spin coating method to form a wet film having a thickness of about 1 μm. The spin condition was 2000 seconds per minute for 30 seconds.
Subsequently, after prebaking at 100 ° C. (90 seconds) and then 200 ° C. (90 seconds) on a hot plate, final baking is performed in a vertical furnace at 250 ° C. (1 hour) in a nitrogen atmosphere to form a cured film. Obtained. About 1 μL of water was dropped onto the cured film thus obtained, and the contact angle was measured (water repellency evaluation). Moreover, normal decane was dripped at the obtained cured film, and the contact angle was measured (oil repellency evaluation). The contact angle was measured by a droplet method under the condition of 25 ° C. using CA-A (product name) manufactured by Kyowa Interface Science Co., Ltd.

[Heat resistance evaluation]
Using the vacuum dried product (resin powder) obtained in Examples 1 and 2 as a sample, thermogravimetric analysis was performed using MTC1000S (product name) manufactured by Mac Science. As analysis conditions, the temperature was increased from room temperature to 600 ° C. at a rate of 10 ° C. per minute. The results are shown in Table 1.

As shown in the results of Table 1, the prepolymers A and B have good heat resistance. When comparing the prepolymer A and the precursor P2-1 and the prepolymers B to F and P2-2, respectively, the prepolymer A -F significantly improved oil repellency and water repellency.
[Alkali resistance evaluation]
A cured film was formed using a vacuum dried product (resin powder) of the prepolymers G to M obtained in Examples 7 to 13. Subsequently, the obtained cured film was immersed in an alkaline aqueous solution, and the contact angle of the cured film before and after immersion was measured by the following method. The measurement results are shown in Table 2.
The vacuum dried product (resin powder) obtained in Examples 7 to 13 was dissolved in cyclohexanone to form a 15 wt% solution, and the solution was filtered through a PTFE (tetrafluoroethylene resin) filter having a pore diameter of 0.5 μm. . The obtained filtrate was applied onto glass by a spin coating method to form a wet film having a thickness of about 1 μm. The spin condition was 2000 seconds per minute for 30 seconds.
Subsequently, after prebaking at 100 ° C. (90 seconds) with a hot plate, final baking was performed in a vertical furnace at 200 ° C. (1 hour) in a nitrogen atmosphere to obtain a cured film. About 1 μL of water was dropped onto the cured film thus obtained, and the contact angle was measured (water repellency evaluation). Further, normal decane and xylene were dropped onto the obtained cured film to measure the contact angle (evaluation of oil repellency). The contact angle was measured by a droplet method using DM700 (product name) manufactured by Kyowa Interface Science Co., Ltd. at 25 ° C.
A cured film obtained by the same method as described above was immersed in a 0.1 mol / L sodium hydroxide aqueous solution and then heated at 60 ° C. for 3 days. Then, after cooling and washing with pure water, it was dried at room temperature, and the contact angle was measured by the same method as described above. The results are shown in Table 2.

  As shown in the results of Table 2, it was found that the prepolymers G to M had good oil repellency and water repellency before and after the alkali test, and had alkali resistance.

Claims (7)

A polymer having a polyaryl ether structure in the main chain, having a crosslinkable functional group, and having a “aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain (P2 And the following general formula (II)

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]
A crosslinkable prepolymer obtained by reacting the alcohol represented by the formula (Q) in the presence of a dehydrofluorinating agent ,
The precursor (P2) is one or both of the following compound (Y-1) and the following compound (Y-2), and the following general formula (1):

[Wherein, n represents an integer of 0 to 2; a and b each independently represents an integer of 0 to 3; Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms; When a plurality of Rf ¹ or Rf ² are present, they may be the same or different from each other; F in the aromatic ring indicates that all the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms. Represent. ]
A fluorine-containing aromatic compound (B) represented by:
A crosslinkable prepolymer, which is a precursor (P21) obtained by subjecting a compound (C) having three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent.
Compound (Y-1): any of compound (Y-1-1) having one crosslinkable functional group and one phenolic hydroxyl group and compound (Y-1-2) having two crosslinkable functional groups and two phenolic hydroxyl groups Either or both.
Compound (Y-2): A compound having a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”. A precursor (P1) which is a polymer having a polyaryl ether structure in the main chain and has “an aromatic ring substituted with a halogen atom capable of reacting with a phenolic hydroxyl group” in the main chain;
The following general formula (II)

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]
In the presence of a dehydrofluorinating agent,
Furthermore, a crosslinkable prepolymer obtained by introducing a crosslinkable functional group by subjecting one or both of the following compound (Y-1) and the following compound (Y-2) to a condensation reaction in the presence of a dehydrofluorinating agent. A polymer ,
The precursor (P1) is represented by the following general formula (1)

[Wherein, n represents an integer of 0 to 2; a and b each independently represents an integer of 0 to 3; Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms; When a plurality of Rf ¹ or Rf ² are present, they may be the same or different from each other; F in the aromatic ring indicates that all the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms. Represent. ]
A fluorine-containing aromatic compound (B) represented by:
A crosslinkable prepolymer, which is a precursor (P11) obtained by subjecting a compound (C) having three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent.
Compound (Y-1): any of compound (Y-1-1) having one crosslinkable functional group and one phenolic hydroxyl group and compound (Y-1-2) having two crosslinkable functional groups and two phenolic hydroxyl groups Either or both.
Compound (Y-2): A compound having a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”. The following general formula (1)

[Wherein, n represents an integer of 0 to 2; a and b each independently represents an integer of 0 to 3; Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms; When a plurality of Rf ¹ or Rf ² are present, they may be the same or different from each other; F in the aromatic ring indicates that all the hydrogen atoms bonded to the aromatic ring are substituted with fluorine atoms. Represent. ]
A fluorine-containing aromatic compound (B) represented by:
A step (S1) of subjecting a compound (C) having three or more phenolic hydroxyl groups to a condensation reaction in the presence of a dehydrofluorinating agent;
The following compound (Y-1) and the following compounds of either or both (Y-2), to a condensation reaction in the presence of a dehydrofluorination agent, and step (S2) of introducing a crosslinkable functional group,
The following general formula (II)

[Wherein, R ^f represents a fluorine-containing alkyl group having 3 to 50 carbon atoms (however, it may contain an etheric oxygen atom). ]
A step (S3) of reacting an alcohol (Q) represented by the following formula in the presence of a dehydrofluorinating agent to introduce a side chain;
A process for producing a crosslinkable prepolymer, comprising:
Compound (Y-1): any of compound (Y-1-1) having one crosslinkable functional group and one phenolic hydroxyl group and compound (Y-1-2) having two crosslinkable functional groups and two phenolic hydroxyl groups Either or both.
Compound (Y-2): A compound having a crosslinkable functional group and “an aromatic ring substituted with a fluorine atom capable of reacting with a phenolic hydroxyl group”. Cured product formed by curing the crosslinkable prepolymer according to claim 1 or 2. A coating composition comprising the crosslinkable prepolymer according to claim 1 or 2 and a solvent. A coating composition according to claim 5 is applied to a substrate to form a wet film, the solvent in the wet film is removed, and or simultaneously with the removal of the solvent, the crosslinkable prepolymer in the wet film is cured. Cured film obtained by making it. An article having the cured film according to claim 6 .